Addition agent for lubricating oils



Patented M ar30,1943 Q UNITED STATES PATENT oFrrcE Eugene Lieber, StatenIsland, N. Y., assignor to Standard such cyclic groups, in such NoDrawing.

10 Claims.

Oil Development Company, a corporation Delaware Application June 21,1939, Q Serial No. 280,263

This invention relates to the preparation of new compositions of matter,particularlmhigh molecular weight polyketones possessing characteristicswhich make them especially useful It is to be observed that in each ofsuch chain structures is present a repeating structural unit,

frequently containing the group:

0 o as hydrocarbon oil blending agents and lubri- '5 (15 r g eating oilblends of these polyketones.

Certain monoketones containing difierent or and an end 8101191 mixedorganic radicals linked through a keto group have been found to increaseoiliness of ra -clubricating oils. These are oi the general formula:

rat-R wherein R is a ring compound radical, e. g., an aryl orheterocyclic group, and R isan alkyl group. preferably having 11 or morecarbon atoms. Although this class of ketoneshas been proposed for use inquantities of .1 to 1% in waxy oils for depressing of pour points, acareful study of a large number of monoalkyl aryl keto'nes belonging tothis class leads to the conclusion that only a small number of theseketones accomplish this result to any substantial degree, so that theirmain important use depends upon their oiliness imparting properties.

The present invention demonstrates that mixed polyketones are properlyconstituted for eifecting a marked reduction in pour points ofwaxcontaining lubricating oils, particularly ,wihen these compoundscontain a plurality of interlinked cyiclic and aliphatic group with theAnother object is to provide the new class of polyketones thus prepared,chiefly for use as ratio of alkyl to cyclic groups limited to 1:1 I

processes for preparing compounds in this class of polyketones, havingsuperior pour depressing power and represented broadly as containingsome of the following chain structures:

0 0 organic radical, e. g., phenyl, diphenyl, na'phthyl, g B I; I R gthienyl,cyclohexyl,carbazyl, ethyl phenyL'benzyL. etc. By reacting amono ketone of this type with 0 0 a halogen, usually chlorine, or with abi-func- Raisin-las where R represents an 'alkyl group, R" an alkylenegroup, and R, a cyclic group. e. g., aromatic, heterocyclic, alicyclic,or combinations of linearly arranged polyketones.

lubricating oil blending agents.

A further object is to provide lubricating compositions wherein thesepolyketones are blended in sumcient proportions to effect desirableimprovements in pour characteristics and other qualities.

To accomplish these objects selected compounds which'are reactive oractivated so that they can be properly condensed or polymerized I intopreferred structural arrangements are used. A ketone is suitablyconstituted for condensation into a desired polyketone if it contains nomore than one alkyl group joined through a keto linkage to a cyclicgroup and is provided with an active substitucnt forcoupling with othercyclic groups through keto linkages without increase in the proportionof the alkyl groups to the cyclic groups. Thus activation of amono-alkyl-aryl ketone may involve the substitution of a halogen forhydrogen at the end of the alkyl group or condensation of the ketonewith a diacyl halide.

More generally, mixed mono ketones to be employed as initial. materialsmay be represented by the general formula:

wherein, R is an alkyl radical, and R is a cyclic densed in aFriedel-Crafts reaction yields a dewas prepared as follows:

sired polyketone product. Desired products may be' obtained bycondensing the monoketone with a dicarboxylic acidhalide having two ormore carbon atoms, e. g., as in oxalyl chloride or higher dibasiccompounds, in a Friedel-Crafts reaction.

Another type of initial reactant includes phenolic esters of fattyacids, e. g., phenyl stearate,

or a. rearrangement product thereof, e. g., hy-

droxy phenyl-heptadecyl ketone.

The reaction is brought about between the reactive compounds, per se, orbetween them and relatively less active compounds through the agency ofthe known Friedel-Crafts type-condensing catalysts which include thehalides of aluminum, zinc, iron, boron, tin, and titanium,

ordinarily 'AlCh. Other known types of catalysts may be used. Thesecatalysts are preferably employed in relatively large quantities, forexample, in substantially mole to mole proportionswith the reactants.Since-the reaction is extremely vigorous, the reaction temperature ispreferably controlled by cooling so as not to rise above 300? or 400 F.and the reaction mixture is desirably heated in the presence of asolvent under refluxing conditions. Suitable solvents are compoundssubstantially inert to the reactants and which boil-within the desiredreaction temperature range, as for example, tetrachlorethane, aparafllnic naphtha fraction, or similar saturated and halogenatedhydrocarbons. The reaction polyketone product may then be recoveredpurifled and concentrated by washing the extract and distilling of! morevolatile'materials.

Having outlined the general purposes and mode of obtaining thedesiredproducts, the following examples are included to illustrate in moredetail how the preferred compositions are made,

used, tested, and compare with other compositions.

Example 1 A mono-wax-ketone of naphthalene 280 grams of syntheticwax-fatty acids, was converted to the acid chloride composed principallyof mono carboxylic fatty acids containing'an average. of more than 14carbon atoms per molecule and derived by oxidation of war,

Wax-C by treating with 75 grams of P01: on the water bath. The resultingwax-acid-chloride was decanted from the phosphorous acid into, a mixtureof 128 grams of naphthalene and 500 cc.

t of kerosene as solvent contained in a suitable readded actor. 135grams of MCI: was now slowly AlCla the reaction mixture was heated to100 C. and maintained thereat for 5 hours. After cooling the reactionmixture was neutralized with a mixture of water and alcohol and dilutedwith a further 500 cc. of kerosene. After settling the kerosene extractwas distilled with fire and steam to 600 F. to remove low boilingproducts. The residue comprised a grams of a light-green oil. It will bedesignated hereafter as mono-waxketone of naphthalene.

When 1, 2 and 5% of the mono-wax-ketone of naphthalene," was prepared-asdescribed above, was blended in a waxy-oil, the pour point of which was+30 R, the pour point of each blend was found to be +25 F., +20 F., and+15 F., re-

spectively. l

- Example 2 The mono-wax ketone of naphthalene" was chlorinated bypassing chlorine gas through the ketone maintained at 300..F. in asuitable reactionvessel. The chlorination was continued until 16 percentchlorine by weight had been absorbed.

300 grams of the "chlorinated-mono-waxketone of naphthalene" was placedin a suitable reactor equipped with stirring motor and thermometer. 500cc. of parafiin was added to act as solvent followed by grams ofactivated Attapulgas clay. The agitation was started and the temperatureraised gradually over 2 hours to 500 F. where it was maintained thereatfor 4 hours.

Throughout this period copious volumes of hydrogen chloride was evolved,indicating vigorous polymerization. At the end of the reaction period,the H01 evolution had substantially subsided. The reaction mixture wasthen cooled and diluted with 1 liter of kerosene and filtered free fromclay. The kerosene extract so obtained was distilled with fire and steamto 600 F. to remove low boiling products. A residue comprising 118 gramsof a dark brown viscous oil was obtained as product.

When 1, 2 and 5% of the polymerizationprodnot was blended in waxy-oil,the pour point of which was +30 F., the pour point oi each blend wasfound to be +5 F., --10 F. and l5 FEE,

respectively.

- Example 3 Mono-heptadecyl-naphthyl ketone was prepared from thefollowing proportions of reagents:

Stearlc acid 1 grams 350 pm. do Naphthalene do AlCl: do Solvent cc. ofkerosene-.. 500

with suitable agitation. After the addition of the 75 The procedurefollowed was exactly the same as described under Example 1. A yield of427.2-

grams of mono-heptadecyl-ketone was obtained; when 1, 2 and 5% ofmono-heptadecyl-ketone,

prepared as described above, was blended in-a waxy-oil, the pour pointof which was +30 It, the pour point of each blend was found to be +30"F.', +30 F., and 20 F., respectively.

Example 4 V Mono-heptadecyl-naphthyl ketone was chlorinated bydissolving in tetrachlorethane as solvent chlorine contents,respectively.

and bubbling chlorine gas through while maintaining a temperature of 200F. The chlorination was continued until 10% of chlorine by weight andstill dissolved in the tetrachlorethane was placed in a suitable reactorequipped with agitator and thermometer. The temperature was raised to150 F. and maintained thereat while adding 7.5 grams of AlCla. The A161:was added over a period of 20 minutes. Very vigorous polymerizationensued as evidenced by the very large and rapid evolution of hydrogenchloride. The reaction was allowed to proceed'for 3 hours at 150 F.after the addition of the A1013. The reaction mixture was then cooledand diluted with 800 cc. of kerosene and neutralized with aqueouscaustic solution and alcohol. After settling, the kerosene extract wasdistilled with fire and steam to 700 F. to remove .low boiling products.A residue comprising 125 grams of a deep-green viscous oil was obtained.

Example The procedure of Example 4 was repeated e xactly except that thepolymerization -was carried out in the presence of naphthalene. Thefollowing proportions of reagents were used:

Chlorinated mono-heptadecyl naphthyl -ketone Cl) grams 150 Naphthalenedo Tetrachlorethane as solvent 'cc, 500

AlCla "grams; 7.5

The reaction temperature was maintained initially at 125 F. (3 hrs.) andthen raised to 150 F. for 2 hours. After cooling, the reaction mixturewas diluted with kerosene and neutralized as described in Example 4. Thekerosene extract so obtained was distilled with fire and steam to 600 F.The'residue so obtained comprised 150 grams of a deep green viscous oil.

When 1, 2 and 5% of the residual condensation product was blended in awaxy-oil, the pour point of which was +30'F., the pour point of eachblend was found to be +5: F., -15 1 and --25 F., respectively.

Example 6 In general, the preferred chlorination range was found to bein the region of 10-15% chlorine by weight of the mixed ketone. This wasdetermined as follows:

Mono-heptadecyl naphthyl ketone was chlorinated as described in Example4 to 15 and The resultin chlorinated monoheptadecyl naphthyl ketoneswerepolymerized as further described in Example 4 using the followingconditions:

The yields of product averaged 75%, based on v Reference oil+1% thefollowing table:

to remove solvent and low boiling products.

the chlorinated ketone, for the two polymerizat ons.

The comparative pour depressor potency for three polymeric products madefrom 10, 15, and 20% chloro-ketones respectively is presented in Pourpoint, F. Original oil +30 Original oil+5% polymer (10% chloroketone)Example 4 -20 Original oil+5% polymer (15% chloroketone) Example 6 ---10Original oil+5% polymer (20% chloroketone) Example 6 0 Another importantobservation is that the going examples briefly illustrates the effect ofthe polymerization on the ketones and of the increase in the proportionof cyclic groups to long alkyl groups.

. Pour point, i='.

Reference oil -Q. +30- Reference oil+l1% mono-heptadecylnaphthyl ketone+30 polyketone of Example 4-- Reference oil+2% mono-heptadecylnaphthylketone +30 Reference oil+2% polyketone of Example 4 10 Referenceoil+2% polyketone of Example 5 15 Example 7 Twenty grams of adipic acidwere treated with O Q iHu dissolved in cc. of tetrachlorethane assolvent.- 38 grams of A1013 were then slowly added, while maintainingagitation in a suitable reaction vessel. After the addition of'theAlCla, the reaction mixture washeated to 225 F. and maintained thereatfor 3 hours. After cooling, the reaction mass was poured into analcohol-water mixture and extracted with 500 cc. of kerosene. Thekerosene extract, after washing and settling, was distilled with fireand steam to600 F. in order A bottoms residue of 107 grams of aheavygreen 'oil was obtained as product.

High molecular weight polymers in this residprocedure.

ual condensation product have structures which may be typified by:

the sameblends using mono-stearyl-naphthylketone was obtained:

. Pour point, F. Original oil I +30 Original oil+1% mono stearylnaphthyl ketone Original oil+ 1 adipylated stearyl naphthyl ketone -l5Example 8 The procedure of Example 7 was repeated exactly using thefollowing reagents in the proportions indicated:

Mono-stearyl-phenyl-ketone grams 100- Phthalyl chlor do 20Tetrachlorethane as solvent cc 150 On recovery of the product 78 gramsof a heavy green oil was obtained.

The condensation product results from the reaction of the following twosubstances:

These polymers are accordingly formulated to have the structuresrepresented by:

or similar chains of varying length showing a Polyketone -u CondensationPolymers ratio of less than 1 s'tearyl group to each cyclic group. 7

When 1% of this condensation product was added to a waxy-oil, the pourpoint otwhich was F., the pour point was found to be 0 Fr When 1% ofmono stearyl-phenyl-ketone was added to the same waxy-oil a pan:- pointof. +30 F. was obtained.

Example 9 The procedure of Example 7 was repeated exactly using thefollowing reagents in the proportions indicated:

0' F. When 2% of my condensation product was added to the same-waxy-oil,a pour point of --20 F. was obtained.

When 1%-of the mono-wax-ketone of naphthalene I O -WHX I where the waxrepresents an alkyl radical of average 17 carbon atoms, was added to thesame waxy-oil, a pour point of +25 F. was obtained.

Example 10 The procedure of Example 9 was repeated exactly using thefollowing reagents in the proportions indicated:

Mono-wax-ketone of naphthalene grams 200 Phthalyl chloride do 20Tetrachlorethane as solvent cc 150 A101:

Example 11 7 To 18 grams of phenyl stearate dissolved in 75 cc. oftetrachlorethane was added 18 grams of aluminum chloride. The resultingmixture was placed under a reflux condenser and heated to the boilingpoint of the tetrachlorethane which is substantially 300 F. Refluxingwas continued Mono-wax-ketone of naphthalene grams 100 Phthalyl chloridedo 20 Tetrachlorethane as solvent cc 150 AiCh -grams 30 On recovery ofthe product, 88 grams of a viscous green oil was obtained.

when 1% of thecondensation product was added to a waxy-oil, the pourpoint. of which for three hours thereafter. The reaction mixture wascooled and the catalyst hydrolyzed by the action of aqueous alcohol.Upon addition of kerosene, an oily solution separated from an aqueousand sludge layer. The oily solution was decanted and distilled with fireand steam to a temperature of about 600 F. and the desired highmolecular weight polymer was recovered as a distillation residue. About16 grams of this product was recovered, which makes substantially aquantitative yield of the ester employed..

This product is a light wax-like solid which dissolves freely lnlubricating oils but is insoluble in alcohol, acetone, and similarsolvents.

When 1% of this product was added to a waxy lubricating, oil the pourpoint of which was 30 F.,5 the pour point of the blend was found to beF.

Example 12 18 grams of mixed phenyl esters of acids obtained by airoxidation of paraflln wax was admixed with cc. of tetrachlorethane and 8grams of aluminum chloride. The mixture was refluxed as in Example 11for a period of three hours and the polymer product recovered from thereaction mixture as before. When 1% of the distillation residue wasadded to an oil having a'30 F. pour point, the-blend was found to have apour point of 0 F. when 5% was added to the oil, the pour point wasfound to be depressed to 25 F.

Inthe reaction between the aluminum chloride and the phenol ester of thelong chain fatty acid,

. the acyl-group apparently not only migrates withv in the molecule butalso crosses over to condense was.--l- -30-F., the pour point was foundto be 7b with another phenol ester so as to form a polyketone chainpolymer exhibiting a pour point depressing potency characteristic of thepolyketone containing a higher proportion of aryl I than long chainalkyl groups.

In preparing the reactants for the condensation, it is tobe noted thatcare is taken to select compounds which form substantially linearmolecules wherein cyclic groups are bridged by ketone and aliphaticgroups, and wherein the proportion of alkyl groups to cyclic groups isin a ratio of 1: 1 or less.

One of the eminent advantages gained through the chain reactionformation of the linear polyketones is that it allow more uniformproducts of any limited degree in molecular size to be produced. Thesize of the ployketone molecules can be controlled in the chain reactionby the proportions of active reactants and catalyst under any setreaction conditions. This fact stands out in vention are valuableadditions to the group of known pour point depressants, wax modifiers,

and lubricating oil addition agents. Their prep-v aration is practicaland economical since their.

ingredients are, in general, commercially available.

.their'main use in blends with other lubricating oils such as motorlubricating oils, cable oils, greases, heavy fuels, and the like: thatis, for the I most part, they are to be blended with petroleum contrastto the-miscellaneous factors which must be coped with in reactingheterogeneous types of initial materials which condense in alternative:ways rather than coupling at initially determined active points, suchas provided in chloro-monoalkyl-aryl ketones and the other initialreactants indicated as useful for the present invention. In thereactions used, the purpose is to condense ap propriate monoketones withselected compounds which are relatively more reactive or to condensethese monoketones per se after they are suitably activated in order toproduce polyketones of the required properties and compositions. It ispreferable to produce condensation polymers having molecular weightsranging from about 500 to 2000 a or higher. The reactants are carefullychosen so tract upon then being distilled with fire and steam to 600 F.or 700 F., is reduced to a distillation residue free from catalysts, lowmolecular weight reactants and volatile matter, and is then in conditionto be utilized as a highly effective pour point depressant.

The condensation products prepared as de-v scribed in the examples arehigh molecular weight polyketones containing principally a plurality ofdrocarbon oils,- have no greater volatility than lubricating oils, andin general, have a molecular weight above 500. The crude condensationproducts may. in some instances, contain unreacted compounds which arenot active as pour point depressants. These crude products may be useddirectly in lubricating oils. or the active high molecular weightpolyketones components may be extracted with hydrocarbon solvents asdisclosed in the examples.

. cyclic and keto groups. They are soluble in hy- The products of thepresent invention may be I added to lubricating oils in any desiredproportion. Generally, the preferred proportion for pour pointdepression by the highly active polyketones will be about 1 to 2% butappreciable to more extensive effects are obtained with proportions raning from .2 to 5%, additions above about 1 to 2% being effective toarelatively lower degree. 1

The pour point depressants of the present in.

oils which are moreviscous and higher boiling than kerosene.

They may be employed together with other,

types of blending agents such as oxidation inhibitors, sludgedispersers, corrosion inhibitors,

etc.,'or even to supplement other pour point depressors or otheroiliness agents.

The foregoing description and examples are. intended to be illustrativeonly.

Any modifications or variations which conform to the spirit of'thisinvention are intended to be included within the scope of the claims,which are not intended to be limited by any theory on mechanism by whichthe products are formed and perform their beneficial function, nor toany particular reactants, proportions, nor conditions.

I claim:

1. An improved'lubricant comprising a lubricating oil blended with aminor amount of a high molecular weight polyketone constitutedessentiallyof at least 2 cyclic organic groups interlinked through ketogroups and joined in a chain to an alkyl group through a keto linkage.

2. An improved lubricating oil of low pour point comprising a petroleumhydrocarbon lubricating oilblended with a minor amount of a polyketonehaving a molecular weight of at least 500 composed essentially of atleast 2 cyclic organic groups linearly interlinked in a chain by ketogroups and by-an aliphatic group, the chain having a terminal alkylgroup.

3. An improved lubricating oil of low pour point comprisinga petroleumhydrocarbon lubricating, oil blended with a minor amount of a highmolecular weight polyketone constituted principally by a chain of cyclicorganic groups interconnected through ketone linkages and Joined by ketogroups to terminal alkylgroups, with the number of said terminal alkylgroups to the number of said cyclic groups in a ratio no greater thanabout 1:1.

4. An improved lubricating oil composition of low pour point comprisinga hydrocarbon lubricating oil blended with a minor proportion of apolyketone selected from the class consisting of chloro-alkyl-arylketone condensation polymers, alkyl-aryl-ketone diacyl-halide'condensation polymers, and alkyl oxy-aryl-ketone polymers, which containterminal alkyl groups in a. ratio no greater than about 1:1 to the arylgroups.

5. A composition as described in claim 4, in

which the polyketone is a condensation product 9. A composition asdescribed in claim 4, in-

which the polyketone is a polymerization product of phenyl stearate.

10. A lubricant comprising a' major propor- 10 teger ofat least 1.

tion of a lubricating oil and a. small amount of a high molecular weightpolyketone having the general formula:

in which R is an aromatic group, R is an alkyl group, R" is either analkyiene or arylene group, 'mandm' areeitherflorlandnisasmaliin- EUGENELIEBER.

